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Determining the Chemical Composition of Corrosion Inhibitor/Metal Interfaces with XPS: Minimizing Post Immersion Oxidation
Published on: March 15, 2017
Direct observation of β-chloride elimination from an isolable β-chloroalkyl complex of square-planar nickel
Alex E Carpenter1, Andrew J McNeece, Brandon R Barnett
1Department of Chemistry and Biochemistry, University of California, San Diego , 9500 Gilman Drive, Mail Code 0358, La Jolla, California 92093-0358, United States.
Abstract:
Reported here are the isolation, structural characterization, and decomposition kinetics of the four-coordinate pentachloroethyl nickel complex, NiCl(CCl2CCl3)(CNAr(Mes2))2 (Ar(Mes2) = 2,6-(2,4,6-Me3C6H2)2C6H3). This complex is a unique example of a kinetically persistent β-chloroalkyl in a system relevant to coordination-insertion polymerization of polar olefins. Kinetic analysis of NiCl(CCl2CCl3)(CNAr(Mes2))2 decomposition indicates that β-chloride (β-Cl) elimination proceeds by a unimolecular mechanism that does not require initial dissociation of a CNAr(Mes2) ligand. The results suggest that a direct β-Cl elimination pathway is available to four-coordinate, Group 10 metal vinyl chloride polymerization systems.
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